CA2079535C - Poly hydroxybutyrate/hydroxy-valerate based hot melt adhesive - Google Patents
Poly hydroxybutyrate/hydroxy-valerate based hot melt adhesiveInfo
- Publication number
- CA2079535C CA2079535C CA002079535A CA2079535A CA2079535C CA 2079535 C CA2079535 C CA 2079535C CA 002079535 A CA002079535 A CA 002079535A CA 2079535 A CA2079535 A CA 2079535A CA 2079535 C CA2079535 C CA 2079535C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- adhesive
- plasticizer
- tackifying resin
- hydroxyvalerate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Abstract
Hot melt adhesive compositions are prepared from 20 to 90% by weight of a linearpolyester of 3-hydroxybutyric and 3-hydroxyvaleric acids containing 9 to 35% of the hydroxyvalerate component; 10 to 80% by weight of a polar tackifier having a Ring and Ball softening point (as described by ASTM E-26) greater than about 60°C; 0 to 50% by weight of a plasticizer; 0 to 30% by weight of a wax diluent and 0-3% by weight of a stabilizer; 0-20%
of a compatible polymer. But utilizing a naturally occurring, thermoplastic, biodegradable copolymer as the base polymer, these adhesives advance the state of the art of hot melt adhesives by alleviating the dependence on petroleum based materials and by allowing for the development of hot melt adhesives which either degrade naturally after coming in contact with the soil or which can be composted.
of a compatible polymer. But utilizing a naturally occurring, thermoplastic, biodegradable copolymer as the base polymer, these adhesives advance the state of the art of hot melt adhesives by alleviating the dependence on petroleum based materials and by allowing for the development of hot melt adhesives which either degrade naturally after coming in contact with the soil or which can be composted.
Description
CA 02079~3~ 1997-01-21 POLY HYDROXYBUTYRATE/HYDROXYVALERATE BASED HOT MELT ADHESIVE
Hot melt adhesives are used commercially for a wide variety of applications. Themajor advantage of hot melt adhesive systems is the lack of a carrier fluid which elimin~tes the need for drying the adhesive film once it is applied to the substrate. This elimin~1ion of the drying step overcomes hazards associated with solvent usage and also allows for faster production line speeds. Depending on the desired use, the degree of tack of the hot melt adhesives may be varied over a wide range to produce adhesives varying from pressure sensitive to non-ples~ule sensitive in character. Non-pressure sensitive are used, for example, in bookbinding, bag ending, case and carton sealing. Pressure sensitive hot melts are used in many applications, and particularly in disposables such as diapers, sanitary products and the like, where room temperature tack and long open time are required.
Hot melt adhesives have historically been based on petroleum derived polymers such as polyethylene, ethylene-vinyl acetate, styrenic block copolymers, and poly~ro~ylene to name a few. These compositions are further tackified, plasticized, and reinforced with a variety of resins, oils and waxes which are derived from both petroleum and naturally occurring feedstocks such as wood, gum and tall oil rosin and terpenes. These classic compositions suffer from the cyclical price cycles common to all oil derived materials, and also are generally very resistant to degradation once the articles employing them are disposed of.
The present invention stems from the growing movement away from petroleum derived raw materials to those derived from natural resources and as part of an effort to utilize raw materials which have demonstrated some level of degradation. The present invention utilizes a class of naturally occurring, thermoplastic, biodegradable copolymers derived from a non-petroleum feedstock as the base polymer. Such compositions advance the state of the art of hot melt adhesives by alleviating the dependence on petroleum based materials and by allowing for the development of hot melt adhesives which either degrade naturally after coming in contact with the soil or which can be composted.
It has been discovered that hot melt adhesive compositions suitable for a variety of applications are obtained by use of specific polyhydroxy-butyrate/hydroxy valerate (PHBV) copolymers, tackifiers, and optionally, waxes and/or plasticizers. The adhesives may be CA 02079~3~ 1997-01-21 .
formulated using conventional additives and may vary from pressure sensitive to non-pressure sensitive in character depending upon the desired application.
In its broadest aspect, the present invention is directed to hot melt adhesive compositions comprising 20 to 90% by weight of a linear polyester of 3-hydroxybutyric and 3-hydroxyvaleric acids CO~ inillg 9 to 35% of the hydroxyvalerate component; 10 to 80% by weight of a polar tackifier having a Ring and Ball softening point (as described by ASTM E-26) greater than about 60~C; 0 to 50% by weight of a plasticizer; 0 to 30% by weight of a wax diluent and 0-3% by weight of a stabilizer.
It will be recognized that the general formulations described above can be adapted to include a wide variety of hot melt adhesive compositions, the more precise formulations of which will vary depending upon the specific end use, the knowledge of which is readily available to those skilled in the particular art.
Thus, in general, adhesives can be prepared using 20 to 70% by weight of the polyhydroxy-butyrate/hydroxyvalerate copolymer Col~t~ g 9 to 35% of the hydroxyvalerate component, 10 to 60% of a tackifying resin, 10 to 50% plasticizer and 0 to 3% of a stabilizer.
Preferred pressure sensitive adhesives are prepared using 40 to 50% of a copolymer COI~t~ g 24% of the hydroxyvalerate component; 30 to 50% of a tackifying resin, preferably a terpene phenolic resin; and 20 to 30% of a plasticizer, preferably pycal 94*, a phenyl ether of polyethylene glycol from ICI; or Hercolyn D*, a methyl ester of hydrogenated rosin from Hercules. Lower levels of plasticizer may also be employed to produce adhesives useful for various end uses such as in construction adhesives for disposable products where some initial degree of tack is needed but no residual pressure sensitive properties are required.
In general, non-pressure sensitive adhesives can be prepared using 20-90% by weight of the polyhydroxy-butyrate/hydroxyvalerate copolymer cont~ining 9 to 35% of thehydroxyvalerate component, 10-80% tackifying resin, 0-30% of a wax-like diluent, 0-30%
plasticizer and 0 to 3% of a stabilizer. Preferred non-pres~ule sensitive adhesives are prepared using 50-80% of a copolymer cont~ining 24% of the hydroxyvalerate component;
*This design~tion is used throughout to indicate a trade-mark.
. CA 02079535 1997-01-21 1040% tackifying resin, preferably terpene-phenolic resins or rosin derivatives; 0-25% of a plasticizer, preferably the phenyl ether of polyethylene glycol or the methyl ester of hydrogenated wood rosin; 0-20% of a wax-like diluent, preferably hydrogenated castor oil (also known as castor wax) or 12-hydroxystearamide.
Additionally, compatible polymers other than PHBV may be incorporated into the hot melt adhesives at levels less than about 20% by weight. Representative formulations and applications are discussed hereinbelow and illustrated by the examples, however, these should not be construed as limiting the invention The major component of the a&esive of the invention, present in an amount of 20 to 90% by weight of the adhesive, comprises a linear polyester of 3-hydroxybutyric (HB) and 3-hydroxyvaleric (HV) acids produced from the fermentation of sugars by the bacterium Alcali~enes eutrophus. The general structure is shown below:
~Hz ~ CH3 \ / \ / C C~
I ~ /
HYDROXYVALERATE HYDROXYUVTYr~ATE
(HV) (HB) Polymers suitable for use herein contain 9 to 35% of the hydroxyvalerate component and are available from ICI Americas, Inc. under the Biopol trade-mark.
The tackifying resins useful in the adhesive compositions are generally polar in nature and have a Ring and Ball softening point greater than 60~C and include rosin and rosin derivatives, terpene phenolics, pure phenolic resins, and the like. More particularly, tne useful tackifying resins include any compatible resins or mixtures thereof such as (1) natural and modifled rosins such, for example, as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural and modified rosins, such, for example as the glycerol ester of pale, wood rosin the glycelol cster of hydrogenated rosin, the glycerol ester of polymerized rosln, the CA 02079~3~ 1997-01-21 pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin; (3) phenolic modified terpene resins and hydrogenated derivatives thereof such, for example, as the resin product resulting from the con(l~n~tion, in an acidic medium, of a bicyclic terpene and a phenol; (4) thermoplastic alkyl phenolic resins such as those described in U.S. Patent Nos. 4,073,776 and 4,023,826. Mixtures of two or more of the above described tackifying resins, as well as blends of the above resins with small amounts of (e.g., less than about 10% of the adhesive) less compatible resins may be utilized for some formulations. While the tackifier may comprise up to about 80% of the adhesive, it is generally used in amounts of 10 to 60% by weight.
Depending on the end-use application, and particularly for uses requiring pressure sensitive properties, various compatible plasticizing or extending oils may also be present in the composition. Preferred compatible plasticizers include phth~l~te plasticizers such as dioctyl phth~l~te; liquid polyesters such as Dynacol 720* from Huls; benzoate plasticizers such as 1,4-cyclohexane dimethanol dibenzoate (e.g., Benzoflex 352* available commercially from Velsicol*); phosphate plasticizer such as t-butyl phenyl diphenyl phosphate (e.g., Santicizer 154* available commercially from Monsanto); polyethylene glycols and derivatives thereof such as the phenyl ether of hydrogenated polyethylene glycol (e.g., Pycal 94*
available commercially from ICI) as well as liquid rosin derivatives having Ring and Ball melting points below about 60~C such as the methyl ester of hydrogenated rosin (e.g.
Hercolyn* from Hercules); as well as vegetable and animal oils such as glyceryl esters of fatty acids and polymerization products thereof.
Other applications conventionally employing adhesives based on these PHBV polymers may require the use of wax diluents in order to reduce the melt viscosity or cohesive characteristics of the hot melt adhesive compositions without appreciably decreasing their adhesive bonding characteristics. These waxes are oi~ten used in adhesives which do not exhibit pressure sensitive properties.
Suitable waxes include 12-hydroxy~Lealdmide wax, hydrogenated castor oil, oxidized synthetic waxes, polyethylene oxide having a weight average molecular weight above about 1000 and functionalized synthetic waxes such as carbonyl cont~ining Escomer H101* from Exxon.
CA 02079~3~ 1997-01-21 ~ It should be recognized that some adhesive formulations described herein may contain both wax and plasticizer components so that the presence of one or the other is not mutually excluslve.
Among the applicable stabilizers or antioxidants which may be included herein are high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-cont~ininp phenols. Representative hindered phenols include: 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl)benzene; pentaerythritol tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenol)-propionate; 4,4'-methylenebis (2,6-tert-butylphenol); 4,4'-thiobis (6-tert-butyl-o-cresol); 2,6-di-tertbutylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1,3,5-triazine; di-n-octadecyl 3 ,5-di-tert-butyl-4-hydroxy-benzylphosphonate; 2-(n-octylthio)-ethyl 3 ,S-di-tert-butyl-4-hydroxy-benzoate; and sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-proionate]. If used, the stabilizer is present in levels of about 0.1 to 3% by weight.
Optional additives may be incorporated into the hot melt compositions in order to modify certain properties thereof. Among these additives may be included colorants such as titanium dioxide; and fillers such as talc and clay, etc. There may also be present in the adhesive small amounts (e.g., less than about 20% by weight, and preferably 5 to 20% by weight) of certain thermoplastic polymers such as ethylene vinyl acetate polymers cont~ining 12 to 50% vinyl acetate as well as polycaprolactone polymers. These polymers are employed in order to impart flexibility, toughness and strength.
These hot melt adhesive compositions may be formulated using techniques known inthe art. An exemplary procedure involves placing approximately 40% of the total tackifying resin concentration with all the polyhyroxybutyrate/hydroxyvalerate copolymer, wax, plasticizers and stabilizers in a jacketed mixing kettle, preferably in a jacketed heavy duty mixer, which is equipped with rotors and thereupon raising the temperature to a range of from up to about 190~C. After the resin has melted, the t~ ldl~lre is lowered to 150~ to 165~C.
Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the rem~in~r of the tackifying resin is thoroughly and uniformly admixed therewith.
The adhesives disclosed herein may be employed in a wide variety of uses as are known in the art. The adhesives described herein may be effectively utilized in a variety of CA 02079~3~ 1997-01-21 packaging and carton sealing applications. The non-pressure sensitive a&esives may also be used to bind a plurality of sheets in a wide range of bookbinding operations. When formulated with plasticizers, the resultant adhesives may be used in the assembly or construction of various disposable applications including, but not limited to, sanitary napkins, disposable diapers, hospital gowns, bed pads and the like. In particular, adhesives are useful for the assembly of disposable articles using multi-line construction techniques wherein at least one flexible film substrate is bonded to at least one tissue, non-woven, polyolefin or other flexible polymeric film substrate. In addition, the adhesives may be useful in the bonding of elastic to polyethylene, polypropylene or non-woven substrate so as, for example, to impart elongation resistant gathers thereto. The adhesive may also be utilized in less dem~nl1ing disposable construction applications such as for end or perimeter sealing.
In the following illustrative examples all parts are given by weight and all temperatures in degrees Celsius unless otherwise noted.
EXAMPLE I
In prepal;ng the following samples, a heavy duty mixer which had been heated to 190~C and which was equipped with a stirring paddle was charged with 40% of the tackifying resin, all the antioxidants and the wax. After melting of the resins and wax, stirring was then initiated whereupon the polyester was added slowly at 190~C over a one-half hour period after which the temperature was lowered to 150~C. Heating and stirring were continued until a homogeneous mass was obtained whereupon the remainder of the tackifying resin was admixed therewith.
The samples were tested using the following procedures:
Viscosity measurements were determined after 30 minutes using a Brookfield Viscometer (Spindle 27) at either 160~C or 163~C.
The adhesive was also subjected to Peel/Shear testing such as is conventionally required in the packaging industry. Peel Temperature Test: A bead of test adhesive approximately 1/8 inch in diameter is applied at 300 to 325~F with a glass rod onto 60 pound/ream kraft paper. A second sheet of the same paper is placed in direct alignment with the first sheet within 2 seconds and pressed thereto to form a kraft-to-kraft bond. The bonded -~, CA 02079~3~ 1997-01-21 sheets are then cut perpendicular to the adhesive line into 1 inch wide strips. Duplicate bonded specimens are placed in an oven with one free end of the specimen attached to a fixed support and a 100 gram load suspended from the other free end. The oven temperature is then increased in 10~F increments at 15 minute intervals. The temperature at which bond del~min~tion occurred is specified as the peel temperature.
Shear Temperature Test: Samples are prepared as in peel temperature test but opposite ends of the bonded specimen are suspended and weighted to stress the bond in a shear mode.
The temperature of the oven is increased as in peel test until failure occurs.
X
The compositions and the results of the testing are shown in Tables 1, 2 and 3.
TABLE I
Biopol*(24% HV content) 90 65 B0 60 40 Nirez V-2040 HM 10 35 10 30 60 Escomer H-101 * -- -- 10 10 0 Irganox 1010* 1.0 1.0 1.0 1.0 1.0 Viscosity ~ 163~C rpm 20,650 7,750 12,800 cps N/T 2,250 1,400 7,125 9,075 cps 400 cps 2,100 9,750 6,550 6,625 cps 325 cps 1,975 Adhesion (corrugated) 22~C F.T. F.T. F.T. F.T. No F.T.
Hot melt adhesives are used commercially for a wide variety of applications. Themajor advantage of hot melt adhesive systems is the lack of a carrier fluid which elimin~tes the need for drying the adhesive film once it is applied to the substrate. This elimin~1ion of the drying step overcomes hazards associated with solvent usage and also allows for faster production line speeds. Depending on the desired use, the degree of tack of the hot melt adhesives may be varied over a wide range to produce adhesives varying from pressure sensitive to non-ples~ule sensitive in character. Non-pressure sensitive are used, for example, in bookbinding, bag ending, case and carton sealing. Pressure sensitive hot melts are used in many applications, and particularly in disposables such as diapers, sanitary products and the like, where room temperature tack and long open time are required.
Hot melt adhesives have historically been based on petroleum derived polymers such as polyethylene, ethylene-vinyl acetate, styrenic block copolymers, and poly~ro~ylene to name a few. These compositions are further tackified, plasticized, and reinforced with a variety of resins, oils and waxes which are derived from both petroleum and naturally occurring feedstocks such as wood, gum and tall oil rosin and terpenes. These classic compositions suffer from the cyclical price cycles common to all oil derived materials, and also are generally very resistant to degradation once the articles employing them are disposed of.
The present invention stems from the growing movement away from petroleum derived raw materials to those derived from natural resources and as part of an effort to utilize raw materials which have demonstrated some level of degradation. The present invention utilizes a class of naturally occurring, thermoplastic, biodegradable copolymers derived from a non-petroleum feedstock as the base polymer. Such compositions advance the state of the art of hot melt adhesives by alleviating the dependence on petroleum based materials and by allowing for the development of hot melt adhesives which either degrade naturally after coming in contact with the soil or which can be composted.
It has been discovered that hot melt adhesive compositions suitable for a variety of applications are obtained by use of specific polyhydroxy-butyrate/hydroxy valerate (PHBV) copolymers, tackifiers, and optionally, waxes and/or plasticizers. The adhesives may be CA 02079~3~ 1997-01-21 .
formulated using conventional additives and may vary from pressure sensitive to non-pressure sensitive in character depending upon the desired application.
In its broadest aspect, the present invention is directed to hot melt adhesive compositions comprising 20 to 90% by weight of a linear polyester of 3-hydroxybutyric and 3-hydroxyvaleric acids CO~ inillg 9 to 35% of the hydroxyvalerate component; 10 to 80% by weight of a polar tackifier having a Ring and Ball softening point (as described by ASTM E-26) greater than about 60~C; 0 to 50% by weight of a plasticizer; 0 to 30% by weight of a wax diluent and 0-3% by weight of a stabilizer.
It will be recognized that the general formulations described above can be adapted to include a wide variety of hot melt adhesive compositions, the more precise formulations of which will vary depending upon the specific end use, the knowledge of which is readily available to those skilled in the particular art.
Thus, in general, adhesives can be prepared using 20 to 70% by weight of the polyhydroxy-butyrate/hydroxyvalerate copolymer Col~t~ g 9 to 35% of the hydroxyvalerate component, 10 to 60% of a tackifying resin, 10 to 50% plasticizer and 0 to 3% of a stabilizer.
Preferred pressure sensitive adhesives are prepared using 40 to 50% of a copolymer COI~t~ g 24% of the hydroxyvalerate component; 30 to 50% of a tackifying resin, preferably a terpene phenolic resin; and 20 to 30% of a plasticizer, preferably pycal 94*, a phenyl ether of polyethylene glycol from ICI; or Hercolyn D*, a methyl ester of hydrogenated rosin from Hercules. Lower levels of plasticizer may also be employed to produce adhesives useful for various end uses such as in construction adhesives for disposable products where some initial degree of tack is needed but no residual pressure sensitive properties are required.
In general, non-pressure sensitive adhesives can be prepared using 20-90% by weight of the polyhydroxy-butyrate/hydroxyvalerate copolymer cont~ining 9 to 35% of thehydroxyvalerate component, 10-80% tackifying resin, 0-30% of a wax-like diluent, 0-30%
plasticizer and 0 to 3% of a stabilizer. Preferred non-pres~ule sensitive adhesives are prepared using 50-80% of a copolymer cont~ining 24% of the hydroxyvalerate component;
*This design~tion is used throughout to indicate a trade-mark.
. CA 02079535 1997-01-21 1040% tackifying resin, preferably terpene-phenolic resins or rosin derivatives; 0-25% of a plasticizer, preferably the phenyl ether of polyethylene glycol or the methyl ester of hydrogenated wood rosin; 0-20% of a wax-like diluent, preferably hydrogenated castor oil (also known as castor wax) or 12-hydroxystearamide.
Additionally, compatible polymers other than PHBV may be incorporated into the hot melt adhesives at levels less than about 20% by weight. Representative formulations and applications are discussed hereinbelow and illustrated by the examples, however, these should not be construed as limiting the invention The major component of the a&esive of the invention, present in an amount of 20 to 90% by weight of the adhesive, comprises a linear polyester of 3-hydroxybutyric (HB) and 3-hydroxyvaleric (HV) acids produced from the fermentation of sugars by the bacterium Alcali~enes eutrophus. The general structure is shown below:
~Hz ~ CH3 \ / \ / C C~
I ~ /
HYDROXYVALERATE HYDROXYUVTYr~ATE
(HV) (HB) Polymers suitable for use herein contain 9 to 35% of the hydroxyvalerate component and are available from ICI Americas, Inc. under the Biopol trade-mark.
The tackifying resins useful in the adhesive compositions are generally polar in nature and have a Ring and Ball softening point greater than 60~C and include rosin and rosin derivatives, terpene phenolics, pure phenolic resins, and the like. More particularly, tne useful tackifying resins include any compatible resins or mixtures thereof such as (1) natural and modifled rosins such, for example, as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural and modified rosins, such, for example as the glycerol ester of pale, wood rosin the glycelol cster of hydrogenated rosin, the glycerol ester of polymerized rosln, the CA 02079~3~ 1997-01-21 pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin; (3) phenolic modified terpene resins and hydrogenated derivatives thereof such, for example, as the resin product resulting from the con(l~n~tion, in an acidic medium, of a bicyclic terpene and a phenol; (4) thermoplastic alkyl phenolic resins such as those described in U.S. Patent Nos. 4,073,776 and 4,023,826. Mixtures of two or more of the above described tackifying resins, as well as blends of the above resins with small amounts of (e.g., less than about 10% of the adhesive) less compatible resins may be utilized for some formulations. While the tackifier may comprise up to about 80% of the adhesive, it is generally used in amounts of 10 to 60% by weight.
Depending on the end-use application, and particularly for uses requiring pressure sensitive properties, various compatible plasticizing or extending oils may also be present in the composition. Preferred compatible plasticizers include phth~l~te plasticizers such as dioctyl phth~l~te; liquid polyesters such as Dynacol 720* from Huls; benzoate plasticizers such as 1,4-cyclohexane dimethanol dibenzoate (e.g., Benzoflex 352* available commercially from Velsicol*); phosphate plasticizer such as t-butyl phenyl diphenyl phosphate (e.g., Santicizer 154* available commercially from Monsanto); polyethylene glycols and derivatives thereof such as the phenyl ether of hydrogenated polyethylene glycol (e.g., Pycal 94*
available commercially from ICI) as well as liquid rosin derivatives having Ring and Ball melting points below about 60~C such as the methyl ester of hydrogenated rosin (e.g.
Hercolyn* from Hercules); as well as vegetable and animal oils such as glyceryl esters of fatty acids and polymerization products thereof.
Other applications conventionally employing adhesives based on these PHBV polymers may require the use of wax diluents in order to reduce the melt viscosity or cohesive characteristics of the hot melt adhesive compositions without appreciably decreasing their adhesive bonding characteristics. These waxes are oi~ten used in adhesives which do not exhibit pressure sensitive properties.
Suitable waxes include 12-hydroxy~Lealdmide wax, hydrogenated castor oil, oxidized synthetic waxes, polyethylene oxide having a weight average molecular weight above about 1000 and functionalized synthetic waxes such as carbonyl cont~ining Escomer H101* from Exxon.
CA 02079~3~ 1997-01-21 ~ It should be recognized that some adhesive formulations described herein may contain both wax and plasticizer components so that the presence of one or the other is not mutually excluslve.
Among the applicable stabilizers or antioxidants which may be included herein are high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-cont~ininp phenols. Representative hindered phenols include: 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl)benzene; pentaerythritol tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenol)-propionate; 4,4'-methylenebis (2,6-tert-butylphenol); 4,4'-thiobis (6-tert-butyl-o-cresol); 2,6-di-tertbutylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-1,3,5-triazine; di-n-octadecyl 3 ,5-di-tert-butyl-4-hydroxy-benzylphosphonate; 2-(n-octylthio)-ethyl 3 ,S-di-tert-butyl-4-hydroxy-benzoate; and sorbitol hexa[3-(3,5-di-tert-butyl-4-hydroxyphenyl)-proionate]. If used, the stabilizer is present in levels of about 0.1 to 3% by weight.
Optional additives may be incorporated into the hot melt compositions in order to modify certain properties thereof. Among these additives may be included colorants such as titanium dioxide; and fillers such as talc and clay, etc. There may also be present in the adhesive small amounts (e.g., less than about 20% by weight, and preferably 5 to 20% by weight) of certain thermoplastic polymers such as ethylene vinyl acetate polymers cont~ining 12 to 50% vinyl acetate as well as polycaprolactone polymers. These polymers are employed in order to impart flexibility, toughness and strength.
These hot melt adhesive compositions may be formulated using techniques known inthe art. An exemplary procedure involves placing approximately 40% of the total tackifying resin concentration with all the polyhyroxybutyrate/hydroxyvalerate copolymer, wax, plasticizers and stabilizers in a jacketed mixing kettle, preferably in a jacketed heavy duty mixer, which is equipped with rotors and thereupon raising the temperature to a range of from up to about 190~C. After the resin has melted, the t~ ldl~lre is lowered to 150~ to 165~C.
Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the rem~in~r of the tackifying resin is thoroughly and uniformly admixed therewith.
The adhesives disclosed herein may be employed in a wide variety of uses as are known in the art. The adhesives described herein may be effectively utilized in a variety of CA 02079~3~ 1997-01-21 packaging and carton sealing applications. The non-pressure sensitive a&esives may also be used to bind a plurality of sheets in a wide range of bookbinding operations. When formulated with plasticizers, the resultant adhesives may be used in the assembly or construction of various disposable applications including, but not limited to, sanitary napkins, disposable diapers, hospital gowns, bed pads and the like. In particular, adhesives are useful for the assembly of disposable articles using multi-line construction techniques wherein at least one flexible film substrate is bonded to at least one tissue, non-woven, polyolefin or other flexible polymeric film substrate. In addition, the adhesives may be useful in the bonding of elastic to polyethylene, polypropylene or non-woven substrate so as, for example, to impart elongation resistant gathers thereto. The adhesive may also be utilized in less dem~nl1ing disposable construction applications such as for end or perimeter sealing.
In the following illustrative examples all parts are given by weight and all temperatures in degrees Celsius unless otherwise noted.
EXAMPLE I
In prepal;ng the following samples, a heavy duty mixer which had been heated to 190~C and which was equipped with a stirring paddle was charged with 40% of the tackifying resin, all the antioxidants and the wax. After melting of the resins and wax, stirring was then initiated whereupon the polyester was added slowly at 190~C over a one-half hour period after which the temperature was lowered to 150~C. Heating and stirring were continued until a homogeneous mass was obtained whereupon the remainder of the tackifying resin was admixed therewith.
The samples were tested using the following procedures:
Viscosity measurements were determined after 30 minutes using a Brookfield Viscometer (Spindle 27) at either 160~C or 163~C.
The adhesive was also subjected to Peel/Shear testing such as is conventionally required in the packaging industry. Peel Temperature Test: A bead of test adhesive approximately 1/8 inch in diameter is applied at 300 to 325~F with a glass rod onto 60 pound/ream kraft paper. A second sheet of the same paper is placed in direct alignment with the first sheet within 2 seconds and pressed thereto to form a kraft-to-kraft bond. The bonded -~, CA 02079~3~ 1997-01-21 sheets are then cut perpendicular to the adhesive line into 1 inch wide strips. Duplicate bonded specimens are placed in an oven with one free end of the specimen attached to a fixed support and a 100 gram load suspended from the other free end. The oven temperature is then increased in 10~F increments at 15 minute intervals. The temperature at which bond del~min~tion occurred is specified as the peel temperature.
Shear Temperature Test: Samples are prepared as in peel temperature test but opposite ends of the bonded specimen are suspended and weighted to stress the bond in a shear mode.
The temperature of the oven is increased as in peel test until failure occurs.
X
The compositions and the results of the testing are shown in Tables 1, 2 and 3.
TABLE I
Biopol*(24% HV content) 90 65 B0 60 40 Nirez V-2040 HM 10 35 10 30 60 Escomer H-101 * -- -- 10 10 0 Irganox 1010* 1.0 1.0 1.0 1.0 1.0 Viscosity ~ 163~C rpm 20,650 7,750 12,800 cps N/T 2,250 1,400 7,125 9,075 cps 400 cps 2,100 9,750 6,550 6,625 cps 325 cps 1,975 Adhesion (corrugated) 22~C F.T. F.T. F.T. F.T. No F.T.
4~C F.T. F.T. F.T. F.T. No F.T.
Peel 52~C 71~C 52~C 60~C 54~C
Shear >110~C > 110~C > 110~C > 110~C 54~C
Nirez V-2040 HM* is a terpene-phenolic resin from Arizona Chemical Escomer H-101* is a carbonyl containing functionalized synthetic wax from Exxon.Irganox 1010* is 3n hindered phenol artioxidant from Ciba-Geigy.
N/T: Not Tested _ ~ 8 CA 02079~3~ 1997-01-21 ~Table 1 shows four formulations (1-4) suitable for p~çk~ging applications. The low viscosity of formulation 4 indicates the adhesive would be especially suitable to case and carton sealing applications. Formulation 5, prepared using relatively low levels of the Biopol component, while not suitable for packaging due to poor paperboard adhesion, would be useful for various fugitive or temporary bonding applications.
X
.
Biopol* (24% HV) 80 60 40 70 Nirez V-2040 HM* 10 30 40 l0 Hydrogenated 10 10 20 10 Castor Oil Irganox 1010* 1.0 1.0 1.0 1.0 Viscosity (~ 163~C78,500 at 30,200 at 9,350 at30,100 at 2.5 rpm 2.5 rpm 5 rpm2.5 rpm Adhesion (Corrugated) 22~C F.T. N o F.T. F.T. F.T.
4~C F.T. No F.T. N o F.T.F.T.
Peel 49~C 54~C 93~C 46C~
Shear 132~C 132~C 132~C 62~C
The fiber tear and good heat resistance exhibited by formulations 6 and 9 renders these adhesives particularly suitable for bag ending uses while formulation 8 is especially suited for pac~ in~ and bag applications where cold a&esion is not critical.
CA 02079~3~ 1997-01-21 Biopol* (24% HV) 50 50 26.7 Nirez V-2040 HM* 30 30 30 Pycal 94* 20 -- 21.7 Hercolyn D* -- 20 21.7 Irganox 1010* 0.1 0.1 0.1 Viscosity ~ 163~C 420 cps 655 cps 130 cps (20 rpms) A&esion (corrugated) 22~C F.T. F.T. F.T.
4~C F.T. F.T. N o F.T.
-7~C F.T. F.T. No F.T.
-18~C F.T. F.T. No. F.T.
Peel 31~C 54~C 21~C
Shear >116~C >116~C 91~C
Pycal 94 is a phenyl ether of polyethylene glycol from ICI.
Hercolyn D is a methyl ester of hydrogenated rosin from Hercules.
Formulation 11 is ideally suited for packaging and, more specifically, case and carton sealing due to its low viscosity, good fiber tear, and acceptable peel CA 02079~3~ l997-0l-2l . , and shear values. Formulation 10, although possessing low viscosity, high shear, and good adhesion (fiber tear), exhibits very low peel value which makes it marginal for packaging applications but suitable for palletizing. Formulation 12, prepared with lower levels of the PHBV polymer, exhibits poorer adhesion and lower peel values which make it undesirable for certain packaging applications.
EXAMPLE II
To demonstrate the utility of the invention in the preparation of plasticized adhesives for disposables, a series of statistically controlled formulations was prepared and tested.
The products made were tested for viscosity at 160~C and peel strength.
The peel strength was measured by extruding a single fine line of adhesive (approximately 4 ms/inch) onto polyethylene at 163~C at 100 rpm and bonding with nonwoven at 100 psi for 1 second. This was performed on a laboratory bond maker and bonds were aged 24 hours at 22~C, 50% relative humidity.
Bonds were tested by pulling on Instron Tensile Tester at 12~/min in a 180~
peel with the polyethylene in the stationary jaw.
Nonwoven/nonwoven bonds were made and evaluated in same manner.
The results are shown in Table 4.
CA 02079~3~ 1997-01-21 r Samples A B C D E F
BiopoL (24%) 50 27.5 10 20 22.9 25 Nirez PRL 300 30 50 75 30 44.6 --Hercolyn D 20 22.5 15 50 16.3 25 *
Pycal 94 ~ 16.3 --Irganox 1010 0.1 0.1 0.1 0.1 0.1 0.1 *
Sylvatac Rx -- -- -- -- -- 50 Viscosity at 160~C (cps)¦ 655¦ 515¦ 700 l 200¦ 250l ___ Peel Strength (grams) Polyethylene/NW250 S.F.* 40 S.F.* S.F.* S.F.*
NW/NW S.F.* S.F.* 11 S.F.* S.F.* S.F.*
*Substrate Fa-lure Nirez PRL 300 is a terpene phenolic resin from Arizona Chemical.
Sylvatac Rx is a rosin tackifier from Arizona Chemical.
Samples A, B, C, D and E all demonstrated low viscosity and the required open time, flexibility and wetting to make a substrate destructive bond that is preferred for these disposable applications.
Sample C, containing lower levels of the Biopol component, had a low visco~sity-~but was very brittle and did not make a satisfactory bond for a disposable application.
EXAMPLE III
Based on the test results obtained in Example II, another series of statistica-l:ly controlled adhesive samples was prepared using a preferred narrow range of components and tested as shown in TabLe 5.
-B
CA 02079~3~ 1997-01-21 G H J ~ L
8iopol (24~) 55 ao 50 40 40 Nirez PRL 300 35 40 30 30 50 Hercolyn D ~ 30 --Pycal 94 10 20 20 -- 10 *
Irganox 10100.1 0.1 0.1 0.1 0.1 Viscosity At 160~C ¦ 2300¦ 1115 ¦ 1555 ¦ 1265¦ 1050 180~ Peel (Grams) Polyethylene/NW --- S.F. --- --- S.F.
NW/NW S.F. S.F. S.F. S.F. S.F.
Samples G-~ all demonstrated the required bond performance and were higher in viscosity than Samples A-E, but, except for Sample F, the adhesives were still desirably lower in viscosity than most traditional construction adhesives. This reduced viscosity gives an added benefit of applying the adhesive at lower application temperatures, minimizing the heat history of the product, and decreasing the thermal degradation of the PHBV polymer. The lower coating viscosity also allows more temperature sensitive substrates to be used.
EXAMPLE IV
To show that the adhesives of the invention would have acceptable stability - at- application temperatures of 150~C or less, a thermal stability test was run on a 200 gram sample in a glass jar at 150~C and the viscosity after 30 minutes was tested at various line intervals including the initial.
Biopol (24~) 40 Nirez PRL 300 50 Hercolyn D 10 Irganox 1010 0.1 Initial Viscosity At 135~C (cps) 24,000 Aqed Viscosit~ (cps) at 135~C
After 8 hours at 150~C 26,150 After 12 hours at 150~C 27,750 After 16 hours at 150~C 22,300 After 24 hours at 150~C 15,300 CA 02079~3~ l997-0l-2l This demonstrates that the product has acceptable thermal stability and if the heat history is minimized by lowering application temperatures or using heat on demand systems such as drum unloaders, it will meet processing requirements.
It will be a~parent that various changes and modifications may be made in the embodiments of the invention described above, without department from the scope of the invention, as defined in the appended claims, and it is therefore intended that all matter contained in the foregoing description shall be interpreted as illustrative only an~ not as limitative of the invention.
EXAMPLE V
This example illustrates the use of the PHBV polymers in conjunction with other polymers in the production of useful hot melt adhesives. The components and testing results are shown in Table 6.
lS TABLE 6 M N O
Biopol* 60 60 60 Elvax 40 10 --- ---Vinathene 90500 --- 10 ---Tone 700 --- --- 10 Nirez 300 10 10 10 Hercolyn D 20 20 20 Irganox 1010 0.1 0.1 O.l Viscosity @ 163~C 13,77S cps 22,050 cps 88,500 cps Peel 100~F 100~F lOO~F
Shear - >200~F >200~F 180~F
Adhesion (corrugated) RT F.T. F.T. F.T.
40~F F.T. F.T. F.T.
Heat Stability (24 hrs/350CF) Color B rown B rown B rown Char Very heavy Very heavy Very heavy Gel No No No Skin No No No *
Elvax 40 is an ethylene vinyl acetate copolymer containinq 40% vinyl acetate available from D*uPont.
40 Vinathene 90500 is an ethylene vinyl acetate copolymer containing 50% vinyl U acetate available from Quantum Chemical CA 02079~3~ 1997-01-21 .
Tone 700 is a polycaprolactone polymer available from Union Carbide.
The resulting hot melt adhesives were compatible and well suited for general packaging applications.
EXAMPLE VI
This example illustrates a preferred embodiment of the invention wherein a specific blending procedure is used to produce a workable hot melt adhesive for packaging.
The Biopol, Hercolyn D, and Irganox 1010*were charged to the mixing vessel at 190~C, once melted the temperature was reduced to 163~C. The resin was then added incrementally over about one half hour. Once the resin was all added, the temperature was reduced to 150~C.
P Q
Biopol 60 60 Nirez V-2040 HM 30 ---*
Nirez PRL 300 --- 30 Hercolyn D 10 10 Irganox 1010 0.1 0.1 Viscosity @ 163~C 1,250 cps 5,337 cps Q 150~C 280,000 cps 155,000 cps Peel 140~F 130~F
Shear >200~F >200~F
Adhesion (corrugated) RT F.T. F.T.
40~F F.T. F.T.
Heat Stability (24 Hours/300~F) Color Brown 8rown Char Slight Slight Gel No No Skin Partial Partial The resulting hot melt adhesives possessed excellent characteristics and were especially suited for case and carton sealing applications.
Peel 52~C 71~C 52~C 60~C 54~C
Shear >110~C > 110~C > 110~C > 110~C 54~C
Nirez V-2040 HM* is a terpene-phenolic resin from Arizona Chemical Escomer H-101* is a carbonyl containing functionalized synthetic wax from Exxon.Irganox 1010* is 3n hindered phenol artioxidant from Ciba-Geigy.
N/T: Not Tested _ ~ 8 CA 02079~3~ 1997-01-21 ~Table 1 shows four formulations (1-4) suitable for p~çk~ging applications. The low viscosity of formulation 4 indicates the adhesive would be especially suitable to case and carton sealing applications. Formulation 5, prepared using relatively low levels of the Biopol component, while not suitable for packaging due to poor paperboard adhesion, would be useful for various fugitive or temporary bonding applications.
X
.
Biopol* (24% HV) 80 60 40 70 Nirez V-2040 HM* 10 30 40 l0 Hydrogenated 10 10 20 10 Castor Oil Irganox 1010* 1.0 1.0 1.0 1.0 Viscosity (~ 163~C78,500 at 30,200 at 9,350 at30,100 at 2.5 rpm 2.5 rpm 5 rpm2.5 rpm Adhesion (Corrugated) 22~C F.T. N o F.T. F.T. F.T.
4~C F.T. No F.T. N o F.T.F.T.
Peel 49~C 54~C 93~C 46C~
Shear 132~C 132~C 132~C 62~C
The fiber tear and good heat resistance exhibited by formulations 6 and 9 renders these adhesives particularly suitable for bag ending uses while formulation 8 is especially suited for pac~ in~ and bag applications where cold a&esion is not critical.
CA 02079~3~ 1997-01-21 Biopol* (24% HV) 50 50 26.7 Nirez V-2040 HM* 30 30 30 Pycal 94* 20 -- 21.7 Hercolyn D* -- 20 21.7 Irganox 1010* 0.1 0.1 0.1 Viscosity ~ 163~C 420 cps 655 cps 130 cps (20 rpms) A&esion (corrugated) 22~C F.T. F.T. F.T.
4~C F.T. F.T. N o F.T.
-7~C F.T. F.T. No F.T.
-18~C F.T. F.T. No. F.T.
Peel 31~C 54~C 21~C
Shear >116~C >116~C 91~C
Pycal 94 is a phenyl ether of polyethylene glycol from ICI.
Hercolyn D is a methyl ester of hydrogenated rosin from Hercules.
Formulation 11 is ideally suited for packaging and, more specifically, case and carton sealing due to its low viscosity, good fiber tear, and acceptable peel CA 02079~3~ l997-0l-2l . , and shear values. Formulation 10, although possessing low viscosity, high shear, and good adhesion (fiber tear), exhibits very low peel value which makes it marginal for packaging applications but suitable for palletizing. Formulation 12, prepared with lower levels of the PHBV polymer, exhibits poorer adhesion and lower peel values which make it undesirable for certain packaging applications.
EXAMPLE II
To demonstrate the utility of the invention in the preparation of plasticized adhesives for disposables, a series of statistically controlled formulations was prepared and tested.
The products made were tested for viscosity at 160~C and peel strength.
The peel strength was measured by extruding a single fine line of adhesive (approximately 4 ms/inch) onto polyethylene at 163~C at 100 rpm and bonding with nonwoven at 100 psi for 1 second. This was performed on a laboratory bond maker and bonds were aged 24 hours at 22~C, 50% relative humidity.
Bonds were tested by pulling on Instron Tensile Tester at 12~/min in a 180~
peel with the polyethylene in the stationary jaw.
Nonwoven/nonwoven bonds were made and evaluated in same manner.
The results are shown in Table 4.
CA 02079~3~ 1997-01-21 r Samples A B C D E F
BiopoL (24%) 50 27.5 10 20 22.9 25 Nirez PRL 300 30 50 75 30 44.6 --Hercolyn D 20 22.5 15 50 16.3 25 *
Pycal 94 ~ 16.3 --Irganox 1010 0.1 0.1 0.1 0.1 0.1 0.1 *
Sylvatac Rx -- -- -- -- -- 50 Viscosity at 160~C (cps)¦ 655¦ 515¦ 700 l 200¦ 250l ___ Peel Strength (grams) Polyethylene/NW250 S.F.* 40 S.F.* S.F.* S.F.*
NW/NW S.F.* S.F.* 11 S.F.* S.F.* S.F.*
*Substrate Fa-lure Nirez PRL 300 is a terpene phenolic resin from Arizona Chemical.
Sylvatac Rx is a rosin tackifier from Arizona Chemical.
Samples A, B, C, D and E all demonstrated low viscosity and the required open time, flexibility and wetting to make a substrate destructive bond that is preferred for these disposable applications.
Sample C, containing lower levels of the Biopol component, had a low visco~sity-~but was very brittle and did not make a satisfactory bond for a disposable application.
EXAMPLE III
Based on the test results obtained in Example II, another series of statistica-l:ly controlled adhesive samples was prepared using a preferred narrow range of components and tested as shown in TabLe 5.
-B
CA 02079~3~ 1997-01-21 G H J ~ L
8iopol (24~) 55 ao 50 40 40 Nirez PRL 300 35 40 30 30 50 Hercolyn D ~ 30 --Pycal 94 10 20 20 -- 10 *
Irganox 10100.1 0.1 0.1 0.1 0.1 Viscosity At 160~C ¦ 2300¦ 1115 ¦ 1555 ¦ 1265¦ 1050 180~ Peel (Grams) Polyethylene/NW --- S.F. --- --- S.F.
NW/NW S.F. S.F. S.F. S.F. S.F.
Samples G-~ all demonstrated the required bond performance and were higher in viscosity than Samples A-E, but, except for Sample F, the adhesives were still desirably lower in viscosity than most traditional construction adhesives. This reduced viscosity gives an added benefit of applying the adhesive at lower application temperatures, minimizing the heat history of the product, and decreasing the thermal degradation of the PHBV polymer. The lower coating viscosity also allows more temperature sensitive substrates to be used.
EXAMPLE IV
To show that the adhesives of the invention would have acceptable stability - at- application temperatures of 150~C or less, a thermal stability test was run on a 200 gram sample in a glass jar at 150~C and the viscosity after 30 minutes was tested at various line intervals including the initial.
Biopol (24~) 40 Nirez PRL 300 50 Hercolyn D 10 Irganox 1010 0.1 Initial Viscosity At 135~C (cps) 24,000 Aqed Viscosit~ (cps) at 135~C
After 8 hours at 150~C 26,150 After 12 hours at 150~C 27,750 After 16 hours at 150~C 22,300 After 24 hours at 150~C 15,300 CA 02079~3~ l997-0l-2l This demonstrates that the product has acceptable thermal stability and if the heat history is minimized by lowering application temperatures or using heat on demand systems such as drum unloaders, it will meet processing requirements.
It will be a~parent that various changes and modifications may be made in the embodiments of the invention described above, without department from the scope of the invention, as defined in the appended claims, and it is therefore intended that all matter contained in the foregoing description shall be interpreted as illustrative only an~ not as limitative of the invention.
EXAMPLE V
This example illustrates the use of the PHBV polymers in conjunction with other polymers in the production of useful hot melt adhesives. The components and testing results are shown in Table 6.
lS TABLE 6 M N O
Biopol* 60 60 60 Elvax 40 10 --- ---Vinathene 90500 --- 10 ---Tone 700 --- --- 10 Nirez 300 10 10 10 Hercolyn D 20 20 20 Irganox 1010 0.1 0.1 O.l Viscosity @ 163~C 13,77S cps 22,050 cps 88,500 cps Peel 100~F 100~F lOO~F
Shear - >200~F >200~F 180~F
Adhesion (corrugated) RT F.T. F.T. F.T.
40~F F.T. F.T. F.T.
Heat Stability (24 hrs/350CF) Color B rown B rown B rown Char Very heavy Very heavy Very heavy Gel No No No Skin No No No *
Elvax 40 is an ethylene vinyl acetate copolymer containinq 40% vinyl acetate available from D*uPont.
40 Vinathene 90500 is an ethylene vinyl acetate copolymer containing 50% vinyl U acetate available from Quantum Chemical CA 02079~3~ 1997-01-21 .
Tone 700 is a polycaprolactone polymer available from Union Carbide.
The resulting hot melt adhesives were compatible and well suited for general packaging applications.
EXAMPLE VI
This example illustrates a preferred embodiment of the invention wherein a specific blending procedure is used to produce a workable hot melt adhesive for packaging.
The Biopol, Hercolyn D, and Irganox 1010*were charged to the mixing vessel at 190~C, once melted the temperature was reduced to 163~C. The resin was then added incrementally over about one half hour. Once the resin was all added, the temperature was reduced to 150~C.
P Q
Biopol 60 60 Nirez V-2040 HM 30 ---*
Nirez PRL 300 --- 30 Hercolyn D 10 10 Irganox 1010 0.1 0.1 Viscosity @ 163~C 1,250 cps 5,337 cps Q 150~C 280,000 cps 155,000 cps Peel 140~F 130~F
Shear >200~F >200~F
Adhesion (corrugated) RT F.T. F.T.
40~F F.T. F.T.
Heat Stability (24 Hours/300~F) Color Brown 8rown Char Slight Slight Gel No No Skin Partial Partial The resulting hot melt adhesives possessed excellent characteristics and were especially suited for case and carton sealing applications.
Claims (10)
1. A hot melt adhesive composition comprising 20 to 90% by weight of a linear polyester of 3-hydroxybutyric and 3-hydroxyvaleric acids containing 9 to 35% of the hydroxyvalerate component; 10 to 80% by weight of a polar tackifier having a Ring and Ball softening point (as described by ASTM E-26) greater than about 60°C; 0 to 50% by weight of a plasticizer; 0 to 30% by weight of a wax diluent and 0-3% by weight of a stabilizer; 0-20% of a compatible thermoplastic polymer.
2. The adhesive of Claim 1 wherein the tackifying resin is selected from the group consisting of (1) natural and modified rosins; (2) glycerol and pentaerythritol esters of natural and modified rosins; (3) phenolic modified terpene resins and hydrogenated derivatives thereof; (4) thermoplastic alkyl phenolic resins; and mixtures thereof and the plasticizer is selected from the group consisting of phthalate plasticizers; liquid polyesters; benzoate plasticizers; phosphate plasticizers; polyethylene glycols and derivatives thereof; and liquid rosin derivatives having Ring and Ball melting points below about 60°.
3. The adhesive of Claim 1 wherein the wax is selected from the group consisting of hydroxy stearamide wax, hydrogenated castor oil, oxidized synthetic waxes, polyethylene oxide having a weight average including weight above about 1000 and functionalized synthetic waxes.
4. The adhesive of Claim 1 wherein a thermoplastic polymer selected from the group consisting of ethylene vinyl acetate polymers containing 12 to 50% vinyl acetate and polycaprolactone polymer is present in an amount of 5 to 20% by weight.
5. An adhesive composition comprising 20 to 70% by weight of the polyhydroxy-butyrate/hydroxyvalerate copolymer, containing 9 to 35% of the hydroxyvalerate component, 10 to 60% of a tackifying resin and 10 to 50% plasticizer; 0-20% of a compatible polymer.
6. The adhesive of Claim 5 comprising 40 to 50% of a polyhyroxy-butyrate/hydroxyvalerate copolymer containing 24% of the hydroxyvalerate component; 30 to 50% of a tackifying resin, and 20 to 30% of a plasticizer and 0 to 3% stabilizer.
7. The adhesive of Claim 6 wherein the tackifying resin is a terpene phenolic and the plasticizer is a phenyl ether of polyethylene glycol, or a methyl ester of hydrogenated rosin.
8. A non-pressure sensitive adhesive composition comprising 20-90% by weight of a polyhydroxy-butyrate/hydroxyvalerate copolymer containing 10-80% tackifying resin, 0-30% of a wax-like diluent, 0-30% plasticizer and 0 to 3% stabilizer;
0-20% of a compatible polymer.
0-20% of a compatible polymer.
9. The adhesive of Claim 8 comprising 50-80% by weight of a copolymer containing 24% of the hydroxyvalerate component; 10-40% tackifying resin; 0-20%
waxlike diluent; 0-25% of a plasticizer.
waxlike diluent; 0-25% of a plasticizer.
10. The adhesive of Claim 9 wherein the tackifying resin is a terpene-phenolic resin or rosin derivative, the plasticizer is a phenyl ether of polyethylene glycol or the methyl ester of hydrogenated wood rosin and the wax diluent is hydrogenated castor oil ~. The adhesive of claim 1 wherein the tackifying resin is selected from the group consisting of (1) natural and modified rosins; (2) glycerol and pentaerythritol esters of natural and modified rosins; (3) phenolic modified terpene resins and hydrogenated derivatives thereof; (4) thermoplastic alkyl phenolic resins; and mixtures thereof.
12. The adhesive of claim 1 wherein the plasticizer is selected from the group consisting of phthalate plasticizers; liquid polyesters; benzoate plasticizers; phosphate plasticizers; polyethylene glycols and derivatives thereof; and liquid rosin derivatives having Ring and Ball melting points below about 60°.
12. The adhesive of claim 1 wherein the plasticizer is selected from the group consisting of phthalate plasticizers; liquid polyesters; benzoate plasticizers; phosphate plasticizers; polyethylene glycols and derivatives thereof; and liquid rosin derivatives having Ring and Ball melting points below about 60°.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/826,571 US5169889A (en) | 1992-01-27 | 1992-01-27 | Poly hydroxybutyrate/hydroxyvalerate based hot melt adhesive |
| US826,571 | 1992-01-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2079535A1 CA2079535A1 (en) | 1993-07-28 |
| CA2079535C true CA2079535C (en) | 1998-03-31 |
Family
ID=25246926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002079535A Expired - Fee Related CA2079535C (en) | 1992-01-27 | 1992-09-30 | Poly hydroxybutyrate/hydroxy-valerate based hot melt adhesive |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5169889A (en) |
| EP (1) | EP0553394B1 (en) |
| JP (1) | JPH0662928B2 (en) |
| AU (1) | AU643154B2 (en) |
| CA (1) | CA2079535C (en) |
| DE (2) | DE553394T1 (en) |
| DK (1) | DK0553394T3 (en) |
| ES (1) | ES2067437T3 (en) |
Families Citing this family (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5502158A (en) * | 1988-08-08 | 1996-03-26 | Ecopol, Llc | Degradable polymer composition |
| US5939467A (en) * | 1992-06-26 | 1999-08-17 | The Procter & Gamble Company | Biodegradable polymeric compositions and products thereof |
| EP0618948A1 (en) * | 1992-10-29 | 1994-10-12 | National Starch and Chemical Investment Holding Corporation | Polylactide containing hot melt adhesive |
| US5252646A (en) * | 1992-10-29 | 1993-10-12 | National Starch And Chemical Investment Holding Corporation | Polylactide containing hot melt adhesive |
| US5312850A (en) * | 1993-01-04 | 1994-05-17 | National Starch And Chemical Investment Holding Corporation | Polylactide and starch containing hot melt adhesive |
| US5910520A (en) * | 1993-01-15 | 1999-06-08 | Mcneil-Ppc, Inc. | Melt processable biodegradable compositions and articles made therefrom |
| GB9311399D0 (en) * | 1993-06-02 | 1993-07-21 | Zeneca Ltd | Polyester composition |
| GB9314577D0 (en) * | 1993-07-14 | 1993-08-25 | Zeneca Ltd | Adhesion process |
| DE69422053T2 (en) | 1993-10-15 | 2000-06-29 | Fuller H B Licensing Financ | BIODEGRADABLE OR COMPOSTABLE HOT MELT ADHESIVES CONTAINING POLYESTERS BASED ON LACTIC ACID |
| CZ221196A3 (en) * | 1994-01-28 | 1997-01-15 | Procter & Gamble | Biologically degradable copolymer and plastic parts, which contain biologically degradable copolymers of 3-hydroxyhexanoate |
| US5747573A (en) * | 1994-02-07 | 1998-05-05 | H. B. Fuller Licensing & Financing, Inc. | High heat resistant hot melt adhesive |
| US5656367A (en) * | 1994-04-29 | 1997-08-12 | National Starch And Chemical Investment Holding Corporation | Poly(hydroxybutyrate/hydroxyvalerate) copolymers for fiber bonding |
| ES2141953T3 (en) * | 1994-08-12 | 2000-04-01 | Minnesota Mining & Mfg | COMPOSITIONS OF POLY PRESSURE SENSITIVE ADHESIVES (BETA-HIDROXIORGANOATO). |
| DE4430415A1 (en) * | 1994-08-26 | 1996-03-14 | Buna Gmbh | Poly:hydroxy-butyric acid used as permanent contact adhesive |
| US5574076A (en) * | 1995-05-03 | 1996-11-12 | National Starch And Chemical Investment Holding Corporation | Sucrose benzoate as a tackifier for water sensitive or biodegradable hot melt adhesives |
| US5583187A (en) * | 1995-05-03 | 1996-12-10 | National Starch And Chemical Investment Holding Corporation | Hot melt adhesives based on hydroxy-functional polyesters |
| US5750605A (en) * | 1995-08-31 | 1998-05-12 | National Starch And Chemical Investment Holding Corporation | Hot melt adhesives based on sulfonated polyesters |
| ES2136473T3 (en) * | 1996-04-23 | 1999-11-16 | Uzin Utz Ag | RESIN-BASED DISPERSION ADHESIVES. |
| FI963935A (en) * | 1996-10-01 | 1998-04-02 | Upm Kymmene Oy | polymer Composition |
| US5945375A (en) * | 1997-03-31 | 1999-08-31 | Kimberly-Clark Worldwide, Inc. | Thermal dye diffusion coating and substrate |
| US6281166B1 (en) | 1998-02-20 | 2001-08-28 | Kimberly-Clark Worldwide | Thermal dye diffusion coating and substrate |
| US6022947A (en) * | 1998-09-18 | 2000-02-08 | Union Camp Corporation | Light-colored, low molecular weight phenolic-modified rosin esters |
| US6479145B1 (en) * | 1999-09-09 | 2002-11-12 | Regents Of The University Of Minnesota | Biopolymers and biopolymer blends, and method for producing same |
| US6767972B1 (en) * | 2000-09-15 | 2004-07-27 | Eastman Chemical Company | Methods for slowing the degradation rate of biodegradable polymers and biodegradable polymer compositions and compositions thereof |
| US7094840B2 (en) | 2000-10-27 | 2006-08-22 | Metabolix, Inc. | Compositions comprising low molecular weight polyhydroxyalkanoates and methods employing same |
| DE10104004A1 (en) * | 2001-01-31 | 2002-08-08 | Walcher Ulrich | Environmentally friendly composition for the production of film products, as use in the fields of packaging, agricultural films and disposable packaging |
| EP1236753A1 (en) * | 2001-03-02 | 2002-09-04 | Hycail B.V. | Environmentally degradable polymeric compounds, their preparation and use as hot melt adhesive |
| WO2004076582A1 (en) * | 2003-02-21 | 2004-09-10 | Metabolix Inc. | Pha blends |
| US7781539B2 (en) * | 2003-02-21 | 2010-08-24 | Metabolix Inc. | PHA blends |
| DE602004016563D1 (en) * | 2003-12-30 | 2008-10-23 | Metabolix Inc | nucleating |
| BRPI0600782A (en) * | 2006-02-24 | 2007-11-20 | Phb Ind Sa | composition for preparing degradable polyester polyol, process for obtaining polyester, elastomer, foam, paint and adhesive polyols, and degradable foam of a polyester polyol |
| FR2927629B1 (en) * | 2008-02-14 | 2011-07-29 | Bostik Sa | BIODEGRADABLE THERMOFUSIBLE ADHESIVE COMPOSITION. |
| EP2321368B1 (en) * | 2008-09-05 | 2014-01-22 | The Procter and Gamble Company | Hot melt adhesive composition |
| US20110111012A1 (en) * | 2009-11-12 | 2011-05-12 | Hemcon Medical Technologies, Inc. | Nanomaterial wound dressing assembly |
| US8002399B2 (en) * | 2009-12-02 | 2011-08-23 | Xerox Corporation | Solid inks incorporating a polyhydroxyalkanoate compound for enhanced properties |
| JP5921946B2 (en) * | 2012-04-26 | 2016-05-24 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| JP5883344B2 (en) | 2012-04-26 | 2016-03-15 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| US9475930B2 (en) | 2012-08-17 | 2016-10-25 | Metabolix, Inc. | Biobased rubber modifiers for polymer blends |
| JP5925094B2 (en) | 2012-09-27 | 2016-05-25 | ヘンケルジャパン株式会社 | Hot melt adhesive for labels |
| DE102013004909A1 (en) | 2013-03-22 | 2014-10-09 | Jowat Ag | New adhesive compositions based on renewable raw materials and their use |
| DE102013205144A1 (en) | 2013-03-22 | 2014-09-25 | Novamelt GmbH Klebstofftechnologie | Adhesive composition based on optionally modified polylactide, process for their preparation and use of the adhesive composition |
| JP2014234399A (en) * | 2013-05-30 | 2014-12-15 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| JP6057837B2 (en) * | 2013-05-30 | 2017-01-11 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| EP3004225A1 (en) | 2013-05-30 | 2016-04-13 | Metabolix, Inc. | Recyclate blends |
| JP6154725B2 (en) * | 2013-10-24 | 2017-06-28 | ヘンケルジャパン株式会社 | Hot melt adhesive |
| US10611903B2 (en) | 2014-03-27 | 2020-04-07 | Cj Cheiljedang Corporation | Highly filled polymer systems |
| WO2016037062A1 (en) | 2014-09-05 | 2016-03-10 | Henkel IP & Holding GmbH | Hot melt adhesive compositions and use thereof |
| CN108601860A (en) | 2016-02-12 | 2018-09-28 | 金珂生物医疗公司 | Chitosan ultrafine fiber system |
| WO2018007548A1 (en) | 2016-07-07 | 2018-01-11 | Repsol, S.A. | Compositions of polyhydroxyalkanoates and polar polymers |
| GB201718470D0 (en) * | 2017-11-08 | 2017-12-20 | Provost Fellows Found Scholars And The Other Members Of Board Of The College Of The Holy And Undivid | Adhesive formulations |
| JP7368475B2 (en) | 2018-12-21 | 2023-10-24 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Hot melt adhesives and their use |
| AT523099B1 (en) * | 2019-10-21 | 2023-02-15 | Zampetti Max | membrane film |
| AU2022299275A1 (en) * | 2021-06-21 | 2024-01-18 | Beiersdorf Ag | Biodegradable pressure-sensitive adhesive |
| WO2023223689A1 (en) * | 2022-05-16 | 2023-11-23 | 株式会社カネカ | Composition for hot-melt adhesive |
| ES2942331B2 (en) * | 2022-12-29 | 2023-11-15 | Asociacion Investig De Industria Textil Aitex | PROCEDURE FOR THE MANUFACTURE OF A HOT FUSE ADHESIVE AND HOT FUSE ADHESIVE OBTAINED BY SUCH PROCEDURE |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3959062A (en) * | 1972-08-10 | 1976-05-25 | E. I. Du Pont De Nemours And Company | Method of joining surfaces using segmented copolyester adhesive |
| US4156676A (en) * | 1978-03-27 | 1979-05-29 | Chevron Research Company | Hot melt adhesives having improved thermal stability |
| AU560653B2 (en) * | 1981-07-07 | 1987-04-16 | Monsanto Company | 3-hydroxybutyrate polymers |
| US4477654A (en) * | 1981-07-07 | 1984-10-16 | Imperial Chemical Industries Plc | 3-Hydroxybutyrate polymers |
| DE3875367T2 (en) * | 1987-04-28 | 1993-03-25 | Mitsubishi Gas Chemical Co | METHOD FOR PRODUCING A RANDOM COPOLYMER CONTAINING D - (-) - 3-HYDROXYBUTYRATE AND D - (-) - 3-HYDROXYVALERATE UNITS. |
| US4900299A (en) * | 1987-05-11 | 1990-02-13 | Mcneil-Ppc, Inc. | Biodegradable tampon application comprising poly(3-hydroxybutyric acid) |
| NZ224549A (en) * | 1987-05-29 | 1990-04-26 | Ici Australia Operations | Controlled release polymer microspheres containing at least one active agent |
| US4876331A (en) * | 1987-08-18 | 1989-10-24 | Mitsubishi Kasei Corporation | Copolyester and process for producing the same |
-
1992
- 1992-01-27 US US07/826,571 patent/US5169889A/en not_active Expired - Fee Related
- 1992-08-27 DK DK92114636.1T patent/DK0553394T3/en active
- 1992-08-27 DE DE0553394T patent/DE553394T1/en active Pending
- 1992-08-27 ES ES92114636T patent/ES2067437T3/en not_active Expired - Lifetime
- 1992-08-27 AU AU21344/92A patent/AU643154B2/en not_active Ceased
- 1992-08-27 EP EP92114636A patent/EP0553394B1/en not_active Expired - Lifetime
- 1992-08-27 DE DE69203713T patent/DE69203713T2/en not_active Expired - Fee Related
- 1992-09-18 JP JP4249107A patent/JPH0662928B2/en not_active Expired - Lifetime
- 1992-09-30 CA CA002079535A patent/CA2079535C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2079535A1 (en) | 1993-07-28 |
| US5169889A (en) | 1992-12-08 |
| DK0553394T3 (en) | 1995-09-11 |
| DE69203713D1 (en) | 1995-09-07 |
| EP0553394B1 (en) | 1995-07-26 |
| AU2134492A (en) | 1993-07-29 |
| DE69203713T2 (en) | 1996-01-11 |
| ES2067437T1 (en) | 1995-04-01 |
| EP0553394A1 (en) | 1993-08-04 |
| JPH0662928B2 (en) | 1994-08-17 |
| AU643154B2 (en) | 1993-11-04 |
| DE553394T1 (en) | 1995-08-03 |
| JPH05271638A (en) | 1993-10-19 |
| ES2067437T3 (en) | 1995-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2079535C (en) | Poly hydroxybutyrate/hydroxy-valerate based hot melt adhesive | |
| US5312850A (en) | Polylactide and starch containing hot melt adhesive | |
| AU659353B2 (en) | Polylactide containing hot melt adhesive | |
| US5252646A (en) | Polylactide containing hot melt adhesive | |
| AU664142B2 (en) | Hydrophilic hot melt adhesives | |
| US5583187A (en) | Hot melt adhesives based on hydroxy-functional polyesters | |
| JP3949755B2 (en) | Hot melt adhesives based on sulfonated polyester | |
| US5574076A (en) | Sucrose benzoate as a tackifier for water sensitive or biodegradable hot melt adhesives | |
| CA1332649C (en) | Recyclable hot melt adhesive compositions | |
| US4526577A (en) | Disposable article constructions | |
| AU2001241975B2 (en) | Sulfonated copolyester based water-dispersible hot melt adhesive | |
| US5532306A (en) | Water-sensitive rubber-based hot melt adhesives | |
| AU612063B2 (en) | Sprayable hot melt adhesives for case and carton sealing and tray making | |
| US5952405A (en) | Lactide graft copolymers and hot melt adhesives prepared from same | |
| US4944993A (en) | Toughened rubber based hot melt adhesive compositions for disposable applications | |
| US5852117A (en) | Process for making lactide graft copolymers | |
| WO1999013016A1 (en) | The use of natural oils in hot melt adhesives | |
| CA2156658A1 (en) | Hot melt coatings for paper and paperboard | |
| US5360854A (en) | Hot melt pressure sensitive adhesive composition and applications | |
| CN116635499A (en) | Hot melt adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |